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Due to large sulfur (S) content and simple manufacturing techniques, free-standing cathodes for lithium-sulfur (Li−S) batteries are gaining a lot of attention recently. Waste office paper, which is consumed in large quantities annually, was used to make a free-standing paper-based carbon (FPC) substrate, which inherited fiber-like morphology. In addition, reduced graphene oxide (rGO) nanosheets modified FPC (rGO@FPC) host was also prepared by a vacuum filtration method. After S impregnation, the FPC/S and rGO@FPC/S free-standing cathodes were employed in Li−S batteries. The rGO@FPC/S free-standing cathode exhibited extremely competitive electrochemical performance, including a reversible discharge capacity of 315 mAh g⁻¹ at 0.5 C after 500 cycles. This is due to the uniform S distribution, which boosts the utilization ratio, and the significant blocking action for polysulfide ions, which prevents the redox shuttle effect.